Azo dyestuffs and process of making same



stuffs are Patented Feb. 11, 1930 AZO DYESTUFFS AND PROCESS OF ;IMIAKINGSAME No Drawing. Application filed October 5, 1927, Serial No. 224,272,and in Germany October 15, 1926.

Our invention relates to new corresponding probably to the mula:

azo dyestuffs general forwhich are obtainable by combining a diazocompound with an arylide of a 2-arylam'ino- (We cannot say in' whatposition the azo group enters into the naphthalene nucleus.) Our new azodyeders, being soluble in concentrated sulfuric acid with an olivecolor, dyeing, according to the character of the diazo component, woolmilling, being of color lakes and dyeing, so far as they are waterinsoluble, cotton brown to olive to black shades fast to washing whenproduced on mgto the ice color method.

it together with an The hitherto unknown arylides of2-arylamino-8-naphthol-6-carboxylic acids may be prepared for instancein the following manner: 2.6-naphtholcarboxylic acid is sulfonated withconcentrated sulfuric acid and the 8-sulfonic acid separated from thesulfonation mixture is-transformed by the alkali fusion into8-hydroXy-2-naphthol-B-carboxylic acid. By heating this compound with apresence of a condensing agent the corresponding 2-arylamino-8-naphthol-S-c'arboxylic can be converted into its arylides by heatingarylamine for instance with a dehydrating agent in an indifferentdiluent according toU. S. A. Patent No. 1,101,111. Instead of2.6-naphtholcarboxylic lizeol from the composing, soluble in spirit andwhen dry brown to blackish pdw well soluble in glacial the fibre accordbacid is obtained, which acid one may also start from 2-naphthylamine--carboxylic acid.

The anilide of 2-phenylamino-S-naphthol- 6-carboxylic acid, forinstance, forms an olive brown powder, which can not be recrystalusualorganic solvents. It decomposes at about 170 C It is insoluble inbenzene, soluble in spirit and glacial acetic acid. The para-anisidideof 2-phenylaminos8- naphthol 6-carboxylic acid is an olive greenpowder,'melting at about 160 C. while deglacial acetic acid, littlesoluble in benzene. We could not recrystallize it hitherto.

The fi-napl1thalide of 2-phenylarnino-8- naphthol-B-carboxylic acid isobtained as yeI-' lowish green powder, melting at 170- 175 (3.,insoluble in benzene, little soluble in spirit, acetic acid. We couldndt recrystallize it hitherto;

In order to further illustrate our invention the following examples aregiven, the parts eing by weight and all temperatures in centigradedegrees, but it is understood, that our invention is not limited to theparticular products or reacting conditions mentioned therein.

Ewample 1 Well boiled and dried cotton yarn pregnate'd in the mannerusual. for the production of ice colors with a padding solution preparedas customary with addition of Turkey red oil or similar acting agentsand containing 10 gms. of the anilide of Q-phenyl-'amino-8-naphthol-6-carboxylica acid in the litre. lit is developed,dried, if desired, in a diazo solution containing a suficient amountgms. of 3-chloroaniline in the litre, rinsed and soaped.

of acetic acid and 2,5

is im- 5% after having been com The dyestufi thus produced on the fibrecorresponds probably to the formula:

stirring at about a diazo m In this manner a dark olive shade of anexcellent fastnessis obtained.

The following table cont 11 as the shades of dyeings by producing the amv nents as we 1 obtained 1 the vegetable fiber:

ains some further phenyluhmowith an excess 23,5 parts ofowed to rundyestufis on being prepared 8 naphthol 6 carboxy lic acid is mixe ofacetic acid and while the ammonium salt o .said diazo ara nitraniline-ortho sulfonic acid is ala solution in the usual manner and most of itsmineral acid being neu- W mwgm Dlazo component 01- i l ha Y .7 as

name b-nltro'fl-toluldlmolthelormula:

' L 9N3 ,Dark olive as I Bid. Orthoaminouotoluene o! the lorumla:

H'N N=N Brownish-black 50 o o I as AmmanOrtho-phouetol-aw-wnaphthylsmine oltheformula:

. I Calls 8. H v 7 {t mam NE: W l-ohlero-fl-toluidine at the lormule: aNH.

Brownollve rue-mud! Malta-mm ol the tel-mule.

N0: Gray-brown If t I l M zb-dl hlmoenmno I v Reddlsh dark brown Mamweompomtolu'dlefiuno-dlphenyhmlne Black 00 p-phfllllde; .m nanmam-Blulsh-blwk 1 J V Emple 2 tralized by adding sodium acetate. When Afinely. divided suspension f 35,4 the combination is" finished, theformed as of the do of 2- dyestufi, corresponding in the form 0 Q of thefree acid probably to the forproduction of color lakes, as well as onthe mula: vegetable fibre.

- fonic or carboxylic acids.

is isolated in the usual dark brown shades dyestufi dyeing wo tainedwhen using meta-amino-benzoic In the same manner the ried out with otherarylides of amino 8 naphthol other diazo diazo compounds 0 01 sim1manner: It dyes wool a remarkable to milling. When afterch become fullerwithout cha fastness romed, the dyeings n ingthe shade. A

ar shades is obe diazo compound of acid as diazo component.

6 carboxylic f amino .Ewample 3 process may be car i the 2-arylcompoundsas for instance the -hydroxyarylsulv A tetrazo solution, prepared in theusual containing a suflicien tate f or neutralizing the exces,B-naphthalide of 2- phenyl-amino-8-naphthol-6-carboxylic acid,

' t amount of sodium aces of mineral acid, The separated dyestulfcorresponding probably to the formula:

is filtered oh and well washed. It

in concentrated sulfuric a ish olive color. It used in form of a mixedwith the lake of a good in the followin understood that t ano dyestuffsinclu upon a base,-on a su usual subs fastness.

may paste cidvwith be" advantageously and yields, when trata, a blackcolor dissolves a brownclaims we wish it to be e process of des also thebstratum suita producing roduction 1 dry,

time

brown to blackish powders,

. g I being, when dry,

soluble in concentrated sulfuric acid with an 011V6 color.

2. The process which comprises combining a diazo compound with anarylide of a 2-aryl-amino-8-naphthol-fi-carboxylic acid.

Fibrous materials dyed with the azo dyestufi's claimed in claim 1." v

4. As new compounds the azo dyestufis of V the general formu'l wherein Xmeans S0 or GU, lacing, when brown to blackish powders, soluble inconcentrated sulfuric acid with an olive color and dyeing wool reddishto black shadee which are fast to milling, I 5.1'lhe processwhichcomprises combining a dia-zo compound containing a sulfonic orcarboxylic acid group with an aryli at a2-arylamino-8-naphthol-6carbonylic 6. As new com unds. the dyestu fiscorresponding to e general formula -be' when dry, brown to blackishpowders 10 solu le in concentr ted sulfuric acid with an olive color,and d 'eing wool reddish to black. shades which are fast to milling. 7.As new com ounds the azo dyestuffs corresponding to t e general formula:15

-being when dry., brown toblackish powders soluh e in concentratedsulfuric acid with an olive color, and dyeing wool dark brown shadeswhich are fast to milling. I

' 8. The process which comprises combining a diazotizedaminonitrobenzenesulfonic aci with an arylide of a 2-aryl-amino-8-nahthol-fi-carboxylic acid.

. In testimony whereof, we aflix our signatures.

- LEOPOLD LASKA.

ARTHUR ZITSCHER.

